BLOCK-COPOLYMERS WITH LOW SURFACE-ENERGY SEGMENTS - SILOXANE-MODIFIED AND PERFLUOROALKANE-MODIFIED BLOCKS

In this paper we describe the preparation and preliminary characterization of diblock copolymers with a low surface energy block. These polymers were prepared by modifying the isoprene block in styrene-isoprene-based block copolymers with either short perfluoroalkyl or dimethyl siloxy 'fingers'. Specifically, the diene block of a styrene-isoprene block copolymer containing a large proportion of pendent vinyl groups (1,2- and 3,4-isoprene) was reacted with the appropriate hydrosilane in the presence of non-acidic Pt catalyst. The degree of attachment of hydrosilane was as high as 50% of the pendent unsaturations. Pendent vinyl groups were converted more efficiently than pendent methyl vinyl groups. These block copolymers, when mixed with the styrene homopolymer, exhibited surface segregation behaviour which depended on both polymer molecular weight and processing conditions. The surface segregation properties of the resulting block copolymers were studied by a variety of techniques which include contact and either X-ray photoelectron spectroscopy or Rutherford backscattering spectrometry. Contact angles as high as 110 degrees were measured for both the siloxane- and perfluoroalkane-modified materials.